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At least 289 records · Page 16

State-Based Implicit Coordination and Applications

In air traffic management, pairwise coordination is the ability to achieve separation requirements when conflicting aircraft simultaneously maneuver to solve a conflict. Resolution algorithms are implicitly coordinated if they provide coordinated resolution maneuvers to conflicting aircraft when only surveillance data, e.g., position and velocity vectors, is periodically broadcast by the aircraft. This paper proposes an abstract framework for reasoning about state-based implicit coordination. The framework consists of a formalized mathematical development that enables and simplifies the design and verification of implicitly coordinated state-based resolution algorithms. The use of the framework is illustrated with several examples of algorithms and formal proofs of their coordination properties. The work presented here supports the safety case for a distributed self-separation air traffic management concept where different aircraft may use different conflict resolution algorithms and be assured that separation will be maintained.

Narkawicz, Anthony J.↗

Painleve-gullstrand-type Coordinates for the Five-dimensional Myers-Perry Black Hole

The Painleve-Gullstrand coordinates provide a convenient framework for presenting the Schwarzschild geometry because of their flat constant-time hypersurfaces, and the fact that they are free of coordinate singularities outside r=0. Generalizations of Painlev´e-Gullstrand coordinates suitable for the Kerr geometry have been presented by Doran and Nat´ario. These coordinate systems feature a time coordinate identical to the proper time of zero-angular-momentum observers that are dropped from infinity. Here, the methods of Doran and Nat´ario are extended to the five-dimensional rotating black hole found by Myers and Perry. The result is a new formulation of the Myers-Perry metric. The properties and physical significance of these new coordinates are discussed.

Generalizations↗

Implementation of a Relay Coordination System for the Mars Network

Mars network relay operations involve the coordination of lander and orbiter teams through long-term and short-term planning, tactical changes and post-pass analysis. Much of this coordination is managed through email traffic and point-to-point file data exchanges. It is often difficult to construct a complete and accurate picture of the relay situation at any given moment, as there is no centralized store of correlated relay data. The Mars Relay Operations Service (MaROS) is being implemented to address the problem of relay coordination for current and next-generation relay missions. The service is provided for the purpose of coordinating communications sessions between landed spacecraft assets and orbiting spacecraft assets at Mars. The service centralizes a set of functions previously distributed across multiple spacecraft operations teams, and as such greatly improves visibility into the end-to-end strategic coordination process. Most of the process revolves around the scheduling of communications sessions between the spacecraft during periods of time when a landed asset on Mars is geometrically visible by an orbiting spacecraft. These "relay" sessions are used to transfer data both to and from the landed asset via the orbiting asset on behalf of Earth-based spacecraft operators. This paper will discuss the relay coordination problem space, overview the architecture and design selected to meet system requirements, and describe the first phase of system implementation

Allard, Daniel A.↗

Impact and Estimation of Balance Coordinate System Rotations and Translations in Wind-Tunnel Testing

Discrepancies between the model and balance coordinate systems lead to biases in the aerodynamic measurements during wind-tunnel testing. The reference coordinate system relative to the calibration coordinate system at which the forces and moments are resolved is crucial to the overall accuracy of force measurements. This paper discusses sources of discrepancies and estimates of coordinate system rotation and translation due to machining and assembly differences. A methodology for numerically estimating the coordinate system biases will be discussed and developed. Two case studies are presented using this methodology to estimate the model alignment. Examples span from angle measurement system shifts on the calibration system to discrepancies in actual wind-tunnel data. The results from these case-studies will help aerodynamic researchers and force balance engineers to better the understand and identify potential differences in calibration systems due to coordinate system rotation and translation.

Toro, Kenneth G.↗

Using Distributed Fiber-optic Strain Sensing to Estimate Generalized Modal Coordinates from Flight-test Data

A method for estimating the generalized modal coordinates of an aircraft during flight has been developed. The Fiber-optic Sensing System (FOSS) offers an efficient and cost-effective method of measuring the strain at thousands of points along the wings. The estimation of modal coordinates was implemented as a two-step process. First, a maximum likelihood method is used to estimate the statistical properties of the sensors and generalized modal coordinates. Second, the strain mode shapes from the finite element model are used along with the statistical properties from the first step to estimate the generalized modal coordinates over time. Using simulated data from the X-56A Multi-Utility Technology Testbed (MUTT), different methods of modal coordinate estimation were compared to demonstrate the benefits and weaknesses of each. These were compared against the exact solution and an ordinary least squares (a more traditional method) estimate. Modal coordinate estimation methods were then applied to flight-test data from the X-56A aircraft to show that the method continues to work well with actual test data. The new estimation method provides insights unavailable from more classical approaches.

Jeffrey Ouellette↗

Micrometer to Atomic Scale Characterisation of Primitive Astromaterials Using A Novel Method, Metis-Fa: A Coordinated Atom Probe Tomography, Transmission Electron Microscopy and NanoSIMS Approach

Introduction: Presolar grains preserve isotopic, chemical and microstructural records of physical and chemical processing, and formation mechanisms within a vast range of evolved stellar systems, the interstellar medium, solar nebula and their parent bodies. These evolutionary records are preserved at the micrometric to atomic scale, requiring coordinated studies to expand our understanding of evolutionary processes occurringthroughout ours and external stellar systems [1]. NanoSIMS enabled rapid in situ identification and isotopic characterisation of presolar grains and their stellar origins using 17O/16O and 18O/16O, and 13C/12C isotopic ratios [1]. Coordination with transmission electron microscopy (TEM) revealed crystallographic and localised contextual relationships and quantitively constrained their major and minor compositions [1]. However, trace elements cannot be quantified, the most sensitive geochemical tracers of environmental conditions, essential to unravelling the chemical record of their evolutionary pathway and parent stellar systems [2-3] . Furthermore, owing to the combination of technical limitations (only 5 – 7 isotopes can be measured per NanoSIMS run) and their small grain sizes of 100 nm < 3 μm (with rare exceptions in nanodiamonds (2 nm ≤) and SiC (< 40 μm)), the number of measurable isotopes per grain volume is limited [1,3] . Through more comprehensive isotopic studies of presolar grains, NanoSIMS studies have shown the importance of the latter, identifying Fe and Mg as important indicators of nuclear synthetic processing and their stellar origins, respectively [4- 5]. Coordination of NanoSIMS and Atom Probe Tomography (APT) revealed morphological signatures, and isotopic and chemical signatures at major to trace levels without requirements for preselection of elements [6]. However, crystallographic signatures in localized contextual relationships cannot be measured. Consequently, coordination of NanoSIMS, TEM and APT is essential to gain access to almost all contextual, structural and geochemical signatures within each presolar grain.Transmission electron microscopy requires a 100 nm thin lamella which is unstable in APT and would not produce any viable data. Atom probe tomography requires a needle-shaped specimen which when measured in TEM removes the local context, impacts the quality of the TEM diffraction images due to the shank angle of the needle, and can alter the chemistry of beam sensitive materials from the higher degree of surface exposure at the tip. To address these issues, we developed METIS-Fa (Multi-technical measurements of Electron Transparent materials using an Indium Sandwich - a FIB approach). A novel method which enables coordination of NanoSIMS, TEM and APT for generalized and targeted studies of individual grains, including beam sensitive materials, without compromising sample preparation requirements for TEM and APT. This method requires only indium and a Focus Ion Beam (FIB), minimizing the movement of fragile materials while still enabling preparation of TEM lamella into APT needles. Samples: Initial experimental development and testing of the method occurred at Astromaterials Research and Exploration Science (ARES), Johnson Space Centre (JSC), NASA and APT measurements and needle preparation occurred at JdLC, Curtin University. Synthetic silicate samples were used as analogs for presolar silicates when performing a trial run of the method. Samples were extracted from a polished thin section created at JSC, NASA, comprised of 38 wt.% Si, 17 wt.% FeO, 13 wt.% MgO, 12 wt.% Al, 11 wt.% Ca based on electron microprobe analysis (EMPA) [8] . Experimental details, pressure and temperature conditions were presented in [8] and references therein. Testing of the capability to target individual grains in mineral matrices using this method for acquisition in APT, measured matrix regions in meteoritic thin sections of primitive meteorites. These meteorites and their identified presolar grains for future targeted studies are detailed in [9]. Techniques: The TEM-FIB lamella were prepared using a FIB. An e-beam assisted pt deposition was used as a protective coating for the synthetic and meteoritic samples. When targeting individual grains, a secondary e-beam assisted pt deposition button is placed over the desired grain before the protective coating to denote its location. A JEOL 2500SE field-emission TEM was used for high-resolution imaging, energy-dispersive X-ray (EDX) and electron diffraction data.TheMETIS-Fa method was experimentally designed, tested and executed using a FIB at ARES, JSCNASA. Needles for APT were prepared using the Tescan Lyra3 GM Dual Beam Focus Ion Beam (FIB) Field Emission SEM (FE-SEM) at the JdLC, Curtin University. Atom probe tomography measurements were conducted using a CAMECA Local Electrode Atom Probe, LEAP 4000X HR. Two pure indium needles were analyzed initially to constraining acquisition parameters and stability under the beam. Manual acquisition was required to maintain evaporation of specimen’s at the apex and monitor interactions with measurement parameters. Experimental Design: Indium foil is pressed onto an Al stub with a pneumatic press and mounted into the FIB adjacent to the TEM-FIB lamella of interest. Using a FIB, two indium slices (5 μm x ~300 nm x 3 μm) are extracted from indium foil and aligned with the TEM-FIB lamella before touching the TEM-FIB lamella. Each slice is then attached through cold welding to the FIB-TEM lamella. This approach eliminates the need for chemical treatments and proved effective for aligning the Indium within the region of interest for APT, holding it in place for up to 4 days during testing.Once both indium slices are attached within their pre-determined region per grain targeting requirements, they are gradually melted onto the FIB-TEM lamella.When targeting a specific grain, measurements should be taken of the pt button and its distance from edge to edge of the lamella before and after sandwiching. A secondary button should be placed over the same region after the Indium slices have been attached to improve precision when preparing APT needles. Results: Figure 1 shows two indium slices melted onto a FIB-TEM lamella, adding additional bulk for preparation into APT needles as shown in Figure 2 [7] . The latter was essential so samples could be measured in TEM and APT without compromising sample preparation requirements and consequently data quality and acquisition stability. METIS-Fa proved effective forimproving geometry. Figure 3 shows a successful APTrun of the synthetic silicate. EMPA, TEM and APTshowed no chemical alterations. During targetingtesting, a solar silicate grain was successfully identifiedand measured in TEM, and prepared into an APTneedle. However, the indium was melted too long during sample preparation, causing expansion andformation of internal porosity leading to sample loss.Conclusion: METIS-Fa greatly expands the number of isotopic and chemical signatures measured per grain volume, and enables measurements of contextual, structural, crystallographic, isotopic and geochemical signatures within individual grains. Gaining access to such a vast range of evolutionary signatures required for expanding our understanding of external stellar and planetary systems and the evolution of our solar system. This method was designed for application to a vast range of phases including being sensitive materials and thus provides a way for coordination of NanoSIMS, TEM and APT not just for the study of presolar grains and by extension primitive astromaterials, but studies in a vast range of other fields including the geosciences and material sciences.Acknowledgments: Thankyou to ARES, JSC, NASA; JdLC Curtin University and Space Science Technology Centre for the use of laboratory facilities and funding [confirm].

Nicole D Nevill↗

Porphyrin coordination polymer nanospheres and nanorods

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porphyrin coordination polymer nanospheres and nanorods

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Photoactive devices including porphyrinoids with coordinating additives

Coordinating additives are included in porphyrinoid-based materials to promote intermolecular organization and improve one or more photoelectric characteristics of the materials. The coordinating additives are selected from fullerene compounds and organic compounds having free electron pairs. Combinations of different coordinating additives can be used to tailor the characteristic properties of such porphyrinoid-based materials, including porphyrin oligomers. Bidentate ligands are one type of coordinating additive that can form coordination bonds with a central metal ion of two different porphyrinoid compounds to promote porphyrinoid alignment and/or pi-stacking. The coordinating additives can shift the absorption spectrum of a photoactive material toward higher wavelengths, increase the external quantum efficiency of the material, or both.

36 MATERIALS SCIENCE↗

Tuning Ligand–Coordinated Single Metal Atoms on TiO 2 and their Dynamic Response during Hydrogenation Catalysis

Ligand-coordinated supported catalysts (LCSCs) are of growing interest for heterogeneous single-atom catalysis. Here, the effect of the choice of organic ligand on the activity and stability of TiO 2 -supported single-atom Pt-ligand catalysts was investigated for ethylene hydrogenation. The activity of these catalysts showed a significant dependence on the choice of ligand and also correlated with coordination number for Pt-ligand and Pt-Cl - . Of the three ligands examined in this study, the one with the lowest Pt coordination number, 1,10-phenanthroline-5,6-dione (PDO), showed the lowest reaction temperature and highest reaction rate, likely due to those metal sites being more accessible to reactant adsorption. In-situ X-ray absorption spectroscopy (XAS) experiments showed that the activity also correlated with good heterolytic dissociation of hydrogen, which was supported by OH/OD exchange experiments and was the rate-determining step of the hydrogenation reaction. In these in-situ XAS experiments up to 190 degrees C, the supported Pt-ligand catalyst showed excellent stability against structural and chemical change. Instead of Pt, the PDO ligand could be coordinated with Ir on TiO 2 to form Ir LCSCs that showed slow activation by loss of Ir-Cl bonds, then excellent stability in the hydrogenation of ethylene. Furthermore, these results provide the chance to engineer ligand-coordinated supported catalysts at the single-atom catalyst level by the choice of ligand and enable new applications at relatively high temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hourglass–Shaped Nanocages with Concaved Structures Based on Selective Self–Complementary Coordination Ligands and Tunable Hierarchical Self–Assembly

Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated. Within these 3D structures, the meta-modified terpyridyl unit preferably coordinates with itself to serve as concave part. By changing the arm length of the ligands, hexamer (SA) and tetramer (SB) are obtained respectively. In-depth studies on the assembly mechanism of SA and SB indicate that the dimers could be formed first via self-complementary coordination and play crucial roles in controlling the final structures. Moreover, both SA and SB can go through hierarchical self-assemblies in solution as well as on solid–liquid interface, which are characterized by transmission electron microscope (TEM) and scanning tunneling microscopy (STM). As a result, it is further demonstrated that various higher-order assembly structures can be achieved by tuning the environmental conditions.

3D metallo-supramolecules↗

Connected Vehicle-Based Traffic Signal Coordination

This study presents a connected vehicles (CVs)-based traffic signal optimization framework for a coordinated arterial corridor. The signal optimization and coordination problem are first formulated in a centralized scheme as a mixed-integer nonlinear program (MINLP). The optimal phase durations and offsets are solved together by minimizing fuel consumption and travel time considering an individual vehicle’s trajectories. Due to the complexity of the model, we decompose the problem into two levels: an intersection level to optimize phase durations using dynamic programming (DP), and a corridor level to optimize the offsets of all intersections. In order to solve the two-level model, a prediction-based solution technique is developed. The proposed models are tested using traffic simulation under various scenarios. Compared with the traditional actuated signal timing and coordination plan, the signal timing plans generated by solving the MINLP and the two-level model can reasonably improve the signal control performance. When considering varies vehicle types under high demand levels, the proposed two-level model reduced the total system cost by 3.8% comparing to baseline actuated plan. MINLP reduced the system cost by 5.9%. It also suggested that coordination scheme was beneficial to corridors with relatively high demand levels. For intersections with major and minor street, coordination conducted for major street had little impacts on the vehicles at the minor street.

42 ENGINEERING↗

1-D calcium, 2-D zinc and 3-D manganese coordination polymers derived from pyrazine-2,3,5,6-tetracarboxylic acid

Three coordination polymers were synthesized from pyrazine-2,3,5,6-tetracarboxylic acid (H 4 pztc) in combination with calcium, zinc and manganese ions under hydrothermal conditions and their structures were determined by single crystal X-ray diffraction, powdered X-ray diffraction, Fourier transformed infrared spectroscopy, thermogravimetric and elemental analyses. Structure 1, {(Ca(H 2 pztc)(H 2 O) 3 )n, crystallizes as 1-D chains, with the partially deprotonated ligand in –O,N,O– coordination mode and with the Ca atoms in an uncommon nine coordinate environment. Structure 2, {Zn1(pztc)(H 2 O) 2 Zn2(H 2 O) 4 } n , is an infinite, 2-D coordination network that contains two nonequivalent Zn atoms, each with octahedral geometry, and the fully deprotonated pztc 4- in bis-bridging chelating coordination mode. The stacked 2-D layers are stabilized by extensive inter-layer water-carboxylate hydrogen-bonding with an inter-layer distance of 4.9 Å. Structure 3, {(Mn 2 (pztc)(H 2 O) 2 )} n , is a covalently bonded 3-D network containing two nonequivalent Mn atoms, each with octahedral geometry, and the fully deprotonated pztc 4- units. Structure 3 exhibits paramagnetic behavior at room temperature, and weak antiferromagnetic properties at very low temperature, which is consistent with their nearest Mn…Mn separation distance of 4.9 Å.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coordinated operation of electricity and natural gas systems from day-ahead to real-time markets

Power systems worldwide are becoming more reliant on energy from natural gas, wind, and solar, posing possible reliability and coordination challenges from the tighter coupling of these infrastructure systems. This paper proposes a framework for the market-based coordination of electricity and natural gas system operations. The proposed framework includes a power system model that accounts for flexibility in the commitment of power plants with short start-up and shut-down times, coupled with a dynamic gas model that simulates when gas cannot be delivered to generators. The capabilities of the framework are illustrated using real-world electric power and gas systems, including scenarios around wind and solar penetrations and the analysis of time-variant, “shaped flow” gas nominations. Our results indicate that coordination between power and gas systems improves total gas delivery and reduces out-of-merit order dispatch in the electricity system, and that shaped flows may reduce unserved gas in systems with high penetrations of wind and solar. Coordination can have mixed effects on carbon-dioxide emissions, with emissions increasing with coordination for current systems during high load weeks but decreasing for systems with high renewable penetrations, particularly during periods of high variability.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Predicting boron coordination in multicomponent borate and borosilicate glasses using analytical models and machine learning

Accurate prediction of boron coordination in multicomponent glasses is critical in glass science and technology as it strongly affects the properties of borate and borosilicate glasses. We have collected a dataset containing 657 glasses from literature with boron coordination values and developed models using analytical functions based on the well accepted Dell, Xiao and Bray model. Good prediction of boron coordination with a R 2 value higher than 0.8 was obtained. The large variation of boron coordination from experiments, originated from sample preparations and characterizations, led to difficulties in obtaining models with better prediction performance. Various machine learning (ML) algorithms were evaluated and slightly better prediction performance was observed; however, interpretation of the ML models is less straight forward. In conclusion, this study developed various models capable of providing quantitative boron coordination predictions, providing insights into its structural roles in multi-component glasses, and suggesting fruitful areas for future research.

36 MATERIALS SCIENCE↗

Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox){sub 0.5}(H{sub 2}O)]{sub n}·2n(H{sub 2}O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H{sub 2}sfpip)(ox)(H{sub 2}O){sub 4}]{sub n}·2n(H{sub 2}O) (Ln=Nd (8) Sm (9)), [H{sub 2}ox=oxalic acid, H{sub 3}sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H{sub 3}sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox{sup 2−} anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

36 MATERIALS SCIENCE↗

Coordination Chemistry and f-Element Complexation by Diethylenetriamine- N , N "bis(acetylglycine)- N , N ', N "-triacetic Acid

Here, potentiometric and spectroscopic techniques were used to evaluate the coordination behavior and thermodynamic features of trivalent f-element complexation by diethylenetriamine- N,N" -bis(acetylglycine)- N,N',N" -triacetic acid (DTTA-DAG) and its di(acetylglycine ethyl ester) analogue [diethylenetriamine- N,N" -bis(acetylglycine ethyl ester)- N,N',N" -triacetic acid (DTTA-DAGEE)]. Protonation constants and stability constants of trivalent lanthanide complexes (except Pm 3+ ) were determined by potentiometry. Six protonation sites and three metal–ligand complexes [ML 2– , MHL – , and MH 2 L(aq)] were quantified for DTTA-DAG. Four protonation sites and one metal–ligand complex [ML(aq)] were observed for DTTA-DAGEE, consistent with the presence of two ester groups. Absorption spectroscopy was utilized to measure the stability constants for complexation of trivalent neodymium and americium by DTTA-DAG and trivalent neodymium by DTTA-DAGEE. The coordination environment of trivalent europium in the presence of DTTA-DAG was investigated at various acidities by luminescence lifetime measurements. Decay constants indicate one water molecule in the inner coordination sphere across the 1.0 < pH < 5.5 range, presumably due to octadentate coordination by DTTA-DAG. A trans-lanthanide pattern of complex stabilities for DTTA-DAG was found to be analogous to that observed for DTPA, with a ~10 6 reduction of the complex stability. The lessened strength of complexation, relative to DTPA, was attributed to significant reduction of the total ligand basicity for DTTA-DAG due to the electronic influence of amide functionalization. When DTTA-DAG is used as an aqueous holdback complexant in liquid–liquid distribution experiments, the preferential coordination of Am 3+ in the aqueous environment offers efficient An/Ln differentiation. The separation extends to pH 2 conditions, where the kinetics of phase transfer in such liquid–liquid systems are aided by the acid-catalyzed dissociation of a metal/aminopolycarboxylate complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An europium( iii ) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction

The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu3+ that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O[double bond, length as m-dash]Ca–Cb–O–Cb–Ca[double bond, length as m-dash]O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether O atom bond to Eu3+. Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3]3+ with six 5-membered chelate rings, the six Eu–Ca and six Eu–Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4]- anions are beyond the cationic [Eu(TODGA)3]3+ cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu3+ coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln3+) complexes with tetraalkyldiglycolamide ligands (of the same 1 : 3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln3+ ions in terms of the local structure of Eu3+ in a solid state coordination complex with TODGA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗